Angewandte Chemie,
Год журнала:
2024,
Номер
136(13)
Опубликована: Янв. 19, 2024
Abstract
In
modern
organic
chemistry,
harnessing
the
power
of
multicomponent
radical
reactions
presents
both
significant
challenges
and
extraordinary
potential.
This
article
delves
into
this
scientific
frontier
by
addressing
critical
issue
controlling
selectivity
in
such
complex
processes.
We
introduce
a
novel
approach
that
revolves
around
reversible
addition
thiyl
radicals
to
multiple
bonds,
reshaping
landscape
reactions.
The
key
lies
intricate
interplay
between
reversibility
energy
landscapes
governing
C−C
bond
formation
thiol‐yne‐ene
developed
not
only
allows
prioritize
cascade,
dominating
over
alternative
reactions,
but
also
extends
scope
coupling
products
obtained
from
alkenes
alkynes
various
structures
electron
density
distributions,
regardless
their
relative
polarity
difference,
opening
doors
more
versatile
synthetic
possibilities.
present
study,
we
provide
powerful
tool
for
atom‐economical
C−S
formation,
paving
way
efficient
synthesis
molecules.
Carrying
out
our
experimental
computational
studies,
elucidated
fundamental
mechanisms
underlying
cascades,
knowledge
can
be
broadly
applied
field
chemistry.
Chemical Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 13, 2024
Hypervalent
iodine(III)
compounds
have
found
wide
application
in
modern
organic
chemistry
as
environmentally
friendly
reagents
and
catalysts.
iodine
are
commonly
used
synthetically
important
halogenations,
oxidations,
aminations,
heterocyclizations,
various
oxidative
functionalizations
of
substrates.
Iodonium
salts
arylating
reagents,
while
iodonium
ylides
imides
excellent
carbene
nitrene
precursors.
Various
derivatives
benziodoxoles,
such
azidobenziodoxoles,
trifluoromethylbenziodoxoles,
alkynylbenziodoxoles,
alkenylbenziodoxoles
group
transfer
the
presence
transition
metal
catalysts,
under
metal-free
conditions,
or
using
photocatalysts
photoirradiation
conditions.
Development
hypervalent
catalytic
systems
discovery
highly
enantioselective
reactions
chiral
represent
a
particularly
recent
achievement
field
chemistry.
Chemical
transformations
promoted
by
many
cases
unique
cannot
be
performed
any
other
common,
non-iodine-based
reagent.
This
review
covers
literature
published
mainly
last
7-8
years,
between
2016
2024.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(13)
Опубликована: Янв. 19, 2024
Abstract
In
modern
organic
chemistry,
harnessing
the
power
of
multicomponent
radical
reactions
presents
both
significant
challenges
and
extraordinary
potential.
This
article
delves
into
this
scientific
frontier
by
addressing
critical
issue
controlling
selectivity
in
such
complex
processes.
We
introduce
a
novel
approach
that
revolves
around
reversible
addition
thiyl
radicals
to
multiple
bonds,
reshaping
landscape
reactions.
The
key
lies
intricate
interplay
between
reversibility
energy
landscapes
governing
C−C
bond
formation
thiol‐yne‐ene
developed
not
only
allows
prioritize
cascade,
dominating
over
alternative
reactions,
but
also
extends
scope
coupling
products
obtained
from
alkenes
alkynes
various
structures
electron
density
distributions,
regardless
their
relative
polarity
difference,
opening
doors
more
versatile
synthetic
possibilities.
present
study,
we
provide
powerful
tool
for
atom‐economical
C−S
formation,
paving
way
efficient
synthesis
molecules.
Carrying
out
our
experimental
computational
studies,
elucidated
fundamental
mechanisms
underlying
cascades,
knowledge
can
be
broadly
applied
field
chemistry.
Organic Letters,
Год журнала:
2024,
Номер
26(15), С. 3321 - 3325
Опубликована: Апрель 10, 2024
Asymmetric
sulfonylation
from
a
reaction
of
cyclopropan-1-ol,
sulfur
dioxide,
and
1-(alkynyl)naphthalen-2-ol
in
the
presence
catalytic
amount
organocatalyst
at
room
temperature
is
developed.
Axially
chiral
(S)-(E)-1-(1-(alkylsulfonyl)-2-arylvinyl)naphthalen-2-ols
are
generated
moderate
to
good
yields
with
excellent
enantioselectivity
regioselectivity
under
mild
conditions.
During
this
transformation,
γ-keto
sulfinate
situ
cyclopropan-1-ol
dioxide
acts
as
key
intermediate.
ACS Catalysis,
Год журнала:
2024,
Номер
14(15), С. 11318 - 11331
Опубликована: Июль 15, 2024
Catalytic
enantioselective
borylation
reactions
of
unsaturated
bonds
as
powerful
tools
for
the
synthesis
diverse
chiral
organoboron
compounds
have
gained
much
attention
and
wide
applications
in
various
fields.
However,
atroposelective
arylboration
reaction
with
carbon–carbon
triple
1,3-enynes
to
obtain
axially
1,3-dienylboronates
remains
an
elusive
significant
challenge.
Hence,
we
develop
a
cooperative
copper-
palladium-catalyzed
assemble
plentiful
function
enriched
single
step
from
easily
available
1,3-enynes,
B2pin2,
aryl
bromides
high
levels
chemo-,
regio-,
stereo-,
atroposelectivity.
The
mild
conditions
lead
good
functional
group
tolerance,
which
is
proven
by
broad
substrate
scope
late-stage
functionalizations
bioactive
or
drug
molecules.
Moreover,
can
be
scaled
up,
series
further
transformations
achieved.
It
worth
emphasizing
that
several
olefin
catalysts
ligands
axial
chirality
also
synthesized
through
corresponding
elaborations
such
products,
explains
transformative
ability
application
potential
1,3-dienylboronates.
mechanism
experiment
density
theory
(DFT)
calculations
revealed
process
copper
palladium
catalysis,
indicating
chemoselectivity
regioselectivity
boration
are
determined
enyne
insertion
on
copper,
atroposelectivity
controlled
reductive
elimination
center.
Meanwhile,
calculation
demonstrated
distinct
interactions
between
P═O
C═O
groups
Pd
Bpin
center
key
transition
state
formation
products
varying
configurations
while
employing
identical
configuration
ligands.
ACS Catalysis,
Год журнала:
2024,
Номер
14(4), С. 2429 - 2454
Опубликована: Фев. 1, 2024
Copper-catalyzed
radical
transformations
establish
a
powerful
toolkit
to
construct
versatile
complex
organic
compounds.
The
copper-mediated
bond
formation
step
of
radicals
plays
critical
role
in
controlling
chemo-
and
stereoselectivity
copper-catalyzed
transformation
reactions.
This
involves
three
possible
pathways:
ion-type
formation,
substitution,
reductive
elimination.
review
highlights
the
recent
advances
theoretical
studies
on
mechanisms
models
selectivity
Cu-mediated
radical-involved
providing
general
mechanistic
comprehension
this
key
elementary
copper
catalysis.
A
robust
and
practical
difluoroalkylation
synthon,
α,α-difluoroenol
species,
which
generated
in
situ
from
trifluoromethyl
diazo
compounds
water
the
presence
of
dirhodium
complex,
is
disclosed.
As
compared
to
presynthesized
difluoroenoxysilane
formed
difluoroenolate
under
basic
conditions,
this
difluoroenol
intermediate
displayed
versatile
reactivity,
resulting
dramatically
improved
enantioselectivity
mild
conditions.
demonstrated
catalytic
asymmetric
aldol
reaction
Mannich
reactions
with
ketones
or
imines
chiral
organocatalysts,
quinine-derived
urea,
phosphoric
acid
(CPA),
respectively,
relay
catalysis
strategy
provides
an
effective
platform
for
applying
fluorination
chemistry.
Moreover,
method
features
a
novel
1,2-difunctionalization
process
via
installation
carbonyl
motif
alkyl
group
on
two
vicinal
carbons,
complementary
protocol
metal
carbene
gem-difunctionalization
reaction.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июнь 18, 2024
Abstract
Controlling
regioselectivity
during
difunctionalization
of
alkenes
remains
a
significant
challenge,
particularly
when
the
installation
both
functional
groups
involves
radical
processes.
In
this
aspect,
methodologies
to
install
trifluoromethane
(−CF
3
)
via
have
been
explored,
due
importance
moiety
in
pharmaceutical
sectors;
however,
these
existing
reports
are
limited,
most
which
affording
only
corresponding
β-trifluoromethylated
products.
The
main
reason
for
limitation
arises
from
fact
that
−CF
group
served
as
an
initiator
those
reactions
and
predominantly
preferred
be
installed
at
terminal
(β)
position
alkene.
On
contrary,
functionalization
internal
(α)
would
provide
valuable
products,
but
meticulous
approach
is
necessary
win
switch.
Intrigued
by
we
here
develop
efficient
regioselective
strategy
where
α-position
Molecular
complexity
achieved
simultaneous
insertion
sulfonyl
fragment
(−SO
2
R)
β-position.
A
precisely
regulated
sequence
generation
using
red
light-mediated
photocatalysis
facilitates
switch
position.
Furthermore,
demonstrates
broad
substrate
scope
industrial
potential
synthesis
pharmaceuticals
under
mild
reaction
conditions.
